US20200354829A1 - Methods and apparatuses for forming graphene - Google Patents
Methods and apparatuses for forming graphene Download PDFInfo
- Publication number
- US20200354829A1 US20200354829A1 US16/860,465 US202016860465A US2020354829A1 US 20200354829 A1 US20200354829 A1 US 20200354829A1 US 202016860465 A US202016860465 A US 202016860465A US 2020354829 A1 US2020354829 A1 US 2020354829A1
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- Prior art keywords
- catalyst substrate
- graphene
- gas
- plasma
- carbon source
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- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System or AIIIBV compounds with or without impurities, e.g. doping materials
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- H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
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- H01L21/32051—Deposition of metallic or metal-silicide layers
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- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/182—Graphene
- C01B32/184—Preparation
- C01B32/186—Preparation by chemical vapour deposition [CVD]
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- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/28—Manufacture of electrodes on semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/268
- H01L21/283—Deposition of conductive or insulating materials for electrodes conducting electric current
- H01L21/285—Deposition of conductive or insulating materials for electrodes conducting electric current from a gas or vapour, e.g. condensation
- H01L21/28506—Deposition of conductive or insulating materials for electrodes conducting electric current from a gas or vapour, e.g. condensation of conductive layers
- H01L21/28512—Deposition of conductive or insulating materials for electrodes conducting electric current from a gas or vapour, e.g. condensation of conductive layers on semiconductor bodies comprising elements of Group IV of the Periodic System
- H01L21/28556—Deposition of conductive or insulating materials for electrodes conducting electric current from a gas or vapour, e.g. condensation of conductive layers on semiconductor bodies comprising elements of Group IV of the Periodic System by chemical means, e.g. CVD, LPCVD, PECVD, laser CVD
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- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/324—Thermal treatment for modifying the properties of semiconductor bodies, e.g. annealing, sintering
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- H01L23/52—Arrangements for conducting electric current within the device in operation from one component to another, i.e. interconnections, e.g. wires, lead frames
- H01L23/522—Arrangements for conducting electric current within the device in operation from one component to another, i.e. interconnections, e.g. wires, lead frames including external interconnections consisting of a multilayer structure of conductive and insulating layers inseparably formed on the semiconductor body
- H01L23/532—Arrangements for conducting electric current within the device in operation from one component to another, i.e. interconnections, e.g. wires, lead frames including external interconnections consisting of a multilayer structure of conductive and insulating layers inseparably formed on the semiconductor body characterised by the materials
- H01L23/53204—Conductive materials
- H01L23/53276—Conductive materials containing carbon, e.g. fullerenes
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- H01L29/00—Semiconductor devices adapted for rectifying, amplifying, oscillating or switching, or capacitors or resistors with at least one potential-jump barrier or surface barrier, e.g. PN junction depletion layer or carrier concentration layer; Details of semiconductor bodies or of electrodes thereof ; Multistep manufacturing processes therefor
- H01L29/02—Semiconductor bodies ; Multistep manufacturing processes therefor
- H01L29/12—Semiconductor bodies ; Multistep manufacturing processes therefor characterised by the materials of which they are formed
- H01L29/16—Semiconductor bodies ; Multistep manufacturing processes therefor characterised by the materials of which they are formed including, apart from doping materials or other impurities, only elements of Group IV of the Periodic System
- H01L29/1606—Graphene
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- H01L29/66—Types of semiconductor device ; Multistep manufacturing processes therefor
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- H01L21/70—Manufacture or treatment of devices consisting of a plurality of solid state components formed in or on a common substrate or of parts thereof; Manufacture of integrated circuit devices or of parts thereof
- H01L21/71—Manufacture of specific parts of devices defined in group H01L21/70
- H01L21/768—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics
- H01L21/76838—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics characterised by the formation and the after-treatment of the conductors
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Definitions
- the present disclosure relates to methods of forming graphene, and more particularly, to methods of directly forming graphene on non-catalyst substrates.
- Graphene is a material having a hexagonal honeycomb structure in which carbon atoms are connected two-dimensionally and has a very small, atomic-scale thickness. Graphene has higher electric mobility and excellent heat characteristics compared to silicon (Si), and is also chemically stable and has a broad surface area.
- a method of forming graphene may include providing, in a reaction chamber, a non-catalyst substrate at least partially including a material that does not catalyze growth of graphene, and directly growing graphene on a surface of the non-catalyst substrate based on injecting a reaction gas into the reaction chamber, the reaction gas including a carbon source having an ionization energy equal to or less than about 10.6 eV in a plasma-enhanced chemical vapor deposition (PECVD) process.
- PECVD plasma-enhanced chemical vapor deposition
- the growing of the graphene may be performed at a processing temperature equal to or less than about 400° C.
- the plasma may be generated based on using at least one radio frequency (RF) plasma generator or at least one microwave (MW) plasma generator.
- RF radio frequency
- MW microwave
- the non-catalyst substrate may include at least one of a Group IV semiconductor material, a semiconductor compound, or an insulating material.
- the non-catalyst substrate may further include a dopant.
- the non-catalyst substrate may include a material that includes a combination of at least two elements selected from among Si, Ge, C, Zn, Cd, Al, Ga, In, B, C, N, P, S, Se, As, Sb, or Te.
- the non-catalyst substrate may include at least one of an oxide, a nitride, a carbide of at least one of Si, Ni, Al, W, Ru, Co, Mn, Ti, Ta, Au, Hf, Zr, Zn, Y, Cr, Cu, Mo, or Gd, or a derivative thereof.
- the carbon source may include a hydrocarbon which is in a liquid state at room temperature.
- the carbon source may include at least one of a precursor including a molecular precursor, the molecular precursor including one or more aromatic molecular rings, a precursor including a molecule having one or more aromatic molecular rings and a functional group, a molecular precursor including three or more aliphatic carbon bonds, or a precursor including a functional group.
- the carbon source may include at least one of benzene, toluene, meta-xylene, propane, propene, butane, hexane, octane, cyclohexane, oxygen, nitrogen, sulfur, or phosphor.
- the reaction gas may further include at least one of an inert gas or a reducing gas.
- the graphene may include crystals having a crystal size of about 0.5 nm to about 100 nm.
- the directly growing the graphene may be performed at a pressure that is equal to or less than about 10 Torr.
- the method may further include performing a pre-treatment on a surface of the non-catalyst substrate.
- the performing the pre-treatment may include forming at least one of charges or activation sites that induce adsorption of active carbon radicals on the surface of the non-catalyst substrate.
- the performing the pre-treatment may include injecting a pre-treatment gas into the reaction chamber.
- the pre-treatment gas may include at least one of inert gas, hydrogen, nitrogen, chlorine, fluorine, ammonia, or derivatives thereof.
- An apparatus may include a plasma enhanced chemical vapor deposition machine configured to perform the method.
- the performing the pre-treatment may include supplying a bias power to the non-catalyst substrate, the bias power ranging from about 1 W to about 300 W.
- a method of forming graphene may include pre-treating a surface of a non-catalyst substrate at least partially including a material that does not catalyze growth of graphene, pre-treating including forming at least one of charges or activation sites that induce adsorption of active carbon radicals on the surface of the non-catalyst substrate; and directly growing graphene on the pre-treated surface of the non-catalyst substrate based on injecting a reaction gas into a reaction chamber in which the non-catalyst substrate is provided, the reaction gas including a carbon source having an ionization energy equal to or less than about 10.6 eV in a plasma-enhanced chemical vapor deposition (PECVD) process.
- PECVD plasma-enhanced chemical vapor deposition
- the pre-treating the non-catalyst substrate may include placing the non-catalyst substrate including the pre-treated surface in the reaction chamber, injecting a pre-treatment gas into the reaction chamber, and supplying a bias power to the non-catalyst substrate, the bias power ranging from about 1 W to about 300 W.
- the pre-treatment gas may include at least one of inert gas, hydrogen, nitrogen, chlorine, fluorine, ammonia, or derivatives thereof.
- the growing of the graphene may be performed at a processing temperature equal to or less than about 400° C.
- the plasma may be generated based on using at least one radio frequency (RF) plasma generator or at least one microwave (MW) plasma generator.
- RF radio frequency
- MW microwave
- the non-catalyst substrate may include at least one of a Group IV semiconductor material, a semiconductor compound, or an insulating material.
- the non-catalyst substrate may further include a dopant.
- the non-catalyst substrate may include a material that includes a combination of at least two elements selected from among Si, Ge, C, Zn, Cd, Al, Ga, In, B, C, N, P, S, Se, As, Sb, and Te.
- the non-catalyst substrate may include at least one of an oxide, a nitride, a carbide of at least one of Si, Ni, Al, W, Ru, Co, Mn, Ti, Ta, Au, Hf, Zr, Zn, Y, Cr, Cu, Mo, or Gd, or a derivative thereof.
- the carbon source may include a hydrocarbon which is in a liquid state at room temperature.
- the carbon source may include at least one of a precursor including a molecular precursor, the molecular precursor including one or more aromatic molecular rings, a precursor including a molecule having one or more aromatic molecular rings and a functional group, a molecular precursor including three or more aliphatic carbon bonds, or a precursor including a functional group.
- the carbon source may include at least one of benzene, toluene, meta-xylene, propane, propene, butane, hexane, octane, cyclohexane, oxygen, nitrogen, sulfur, or phosphor.
- the reaction gas may further include at least one of an inert gas or a reducing gas.
- the graphene may include crystals having a crystal size of about 0.5 nm to about 100 nm.
- the directly growing the graphene may be performed at a pressure that is equal to or less than about 10 Torr.
- An apparatus may include a plasma enhanced chemical vapor deposition machine configured to perform the method.
- FIGS. 1A, 1B, and 1C are views of a method of forming graphene, according to some example embodiments
- FIG. 2 is a diagram illustrating ionization energy of each hydrocarbon according to some example embodiments
- FIGS. 3A and 3B are views illustrating a result of the Raman analysis of graphene grown using different carbon sources according to some example embodiments
- FIGS. 4A, 4B, 4C, and 4D are views of a method of forming graphene, according to some example embodiments.
- FIG. 5 is a cross-sectional view of an apparatus for forming graphene according to some example embodiments.
- graphene nanocrystalline graphene
- PECVD plasma-enhanced chemical vapor deposition
- FIGS. 1A, 1B, and 1C are views of a method of forming graphene, according to some example embodiments.
- a reaction gas for growing graphene 190 (e.g., a layer of graphene) ( FIG. 1C ) is injected into a reaction chamber (not shown) in which a non-catalyst substrate 120 is provided (e.g., located), and power to generate plasma is applied (e.g., supplied).
- the non-catalyst substrate 120 is provided in the reaction chamber (e.g., placed in the reaction chamber).
- the non-catalyst substrate 120 includes a substrate formed of (e.g., at least partially comprising) a material that does not catalyze growth of graphene (e.g., is configured to not catalyze growth of graphene).
- the non-catalyst substrate 120 may be configured to not catalyze growth of graphene on an upper surface, surface 120 a , of the non-catalyst substrate 120 .
- the non-catalyst substrate 120 may include a substrate that does not include a metal.
- the non-catalyst substrate 120 may include at least one of a Group IV semiconductor material, a semiconductor compound, or an insulating material.
- the Group IV semiconductor material may include Si, Ge, or Sn.
- the semiconductor compound may include, for example, a material that includes a combination of at least two elements selected from among Si, Ge, C, Zn, Cd, Al, Ga, In, B, C, N, P, S, Se, As, Sb, or Te.
- the insulating material may include at least one of Si, Al, Hf, Zr, Zn, Ti, Ta, W, or Mn or at least one of an oxide, a nitride, a carbide of at least one of Si, Ni, Al, W, Ru, Co, Mn, Ti, Ta, Au, Hf, Zr, Zn, Y, Cr, Cu, Mo, or Gd, or a derivative thereof.
- the non-catalyst substrate 120 may include at least one of an oxide, a nitride, a carbide of at least one of Si, Ni, Al, W, Ru, Co, Mn, Ti, Ta, Au, Hf, Zr, Zn, Y, Cr, Cu, Mo, or Gd, or a derivative thereof.
- the at least one of the oxide, nitride, carbide, or the derivative thereof may further include H.
- the non-catalyst substrate 120 may further include a dopant.
- the materials of the non-catalyst substrate 120 described above are examples, and the non-catalyst substrate 120 may be formed of (e.g., at least partially comprise) a material that does not catalyze the growth of graphene.
- the reaction gas may include a carbon source supplying carbon to grow the graphene 190 .
- the carbon source may be a hydrocarbon having ionization energy equal to or less than about 10.6 eV, for example between about 1.2 eV and about 10.6 eV.
- the carbon source may include a liquid precursor, which is in a liquid state at room temperature.
- the carbon source may include a hydrocarbon which is in a liquid state at room temperature (e.g., about 20° C. to about 25° C.).
- the liquid precursor may be a molecular precursor including one or more aromatic molecular rings such as benzene, toluene, xylene, mesitylene, or the like or a precursor including a molecule having one or more aromatic molecular rings, such as chlorobenzene or anisole (methyl phenyl ether), and a functional group.
- the carbon source may include a molecular precursor including three or more aliphatic carbon bonds such as propane, propene, butane, hexane, octane, cyclohexane, or the like and a precursor including a functional group such as oxygen, nitrogen, sulfur, or the like.
- the carbon source may include at least one of benzene, toluene, meta-xylene, propane, propene, butane, hexane, octane, cyclohexane, oxygen, nitrogen, sulfur, or phosphor.
- any hydrocarbon having ionization energy of about 10.6 eV or less e.g., between about 1.2 eV and about 10.6 eV
- the reaction gas may further include at least one of an inert gas or a hydrogen gas.
- the inert gas may include, for example, at least one of argon gas, neon gas, nitrogen gas, helium gas, krypton gas, or xenon gas.
- FIG. 1A shows an example in which the reaction gas includes a carbon source, inert gas, and hydrogen gas, wherein meta-xylene is used as the carbon source and argon gas is used as the inert gas.
- a mixing ratio of the reaction gas injected into the reaction chamber may be variously modified according to the growth conditions of the graphene.
- power for generating plasma is applied (e.g., supplied) to the reaction chamber from a plasma power supply (not shown).
- the power for generating plasma may be about 10 W to about 4,000 W.
- the power is not limited thereto.
- a radio frequency (RF) plasma generator or a microwave (MW) plasma generator may be used.
- the plasma-enhanced chemical vapor deposition (PECVD) process may utilize a plasma that may be generated based on using at least one radio frequency (RF) plasma generate or at least one microwave (MW) plasma generator.
- the RF plasma generator may generate RF plasma having a frequency range of, for example, about 3 MHz to about 100 MHz
- the MW plasma generator may generate MW plasma having a frequency range of, for example, about 0.7 to about 2.5 GHz.
- the frequency ranges above are examples, and other frequency ranges may also be used.
- a plurality of RF plasma generators or a plurality of MW plasma generators may be used as a plasma power supply.
- a mixing ratio of reaction gases injected into the reaction chamber that is, a volume ratio of a carbon source, an inert gas, and a hydrogen gas may be, for example, approximately about 1:about 0.01 to about 5,000:about 0 to about 300.
- the volume ratio of the carbon source, the inert gas, and the hydrogen gas included in the reaction gas may be appropriately adjusted according to different growth conditions.
- a processing temperature for growing graphene may be equal to or less than about 400° C., which is lower than a temperature used in a chemical vapor deposition (CVD) process.
- a processing temperature in the reaction chamber may be about 180° C. to about 400° C.
- a processing pressure for growing graphene may be equal to or less than about 10 Torr.
- the processing pressure may be about 0.001 Torr to about 10 Torr.
- the above-described processing pressure is an example, and other processing pressures may also be used.
- active carbon radicals (C*) are generated by plasma of a reaction gas, in which a carbon source, an inert gas, and a hydrogen gas are mixed and are adsorbed onto a surface of the non-catalyst substrate 120 .
- a carbon source has ionization energy of about 10.6 eV
- active carbon radicals (C*) are easily generated at a relatively low temperature, and the active carbon radicals (C*) are adsorbed onto the surface of the non-catalyst substrate 120 to activate the surface of the non-catalyst substrate 120 .
- the graphene 190 may be grown on the surface of the non-catalyst substrate 120 .
- the ionization energy of the carbon source is as low as 10.6 eV
- active carbon radicals may be easily generated even at a low temperature, for example, at a temperature equal to or less than about 400° C. (e.g., about 180° C. to about 400° C.).
- the graphene 190 may be directly grown on the surface 120 a of the non-catalyst substrate 120 .
- the grown graphene may include nano-scale crystals.
- the graphene 190 may include crystals having a size equal to or less than about 100 nm.
- the graphene 190 may include crystals having a size of about 0.5 nm to about 100 nm.
- a method of forming graphene may include providing, in a reaction chamber, a non-catalyst substrate 120 at least partially including a material that does not catalyze growth of graphene; and directly growing graphene 190 on a surface 120 a of the non-catalyst substrate 120 ( FIG. 1C ) based on injecting a reaction gas into the reaction chamber ( FIG. 1A ), the reaction gas including a carbon source having an ionization energy equal to or less than about 10.6 eV in a plasma-enhanced chemical vapor deposition (PECVD) process.
- PECVD plasma-enhanced chemical vapor deposition
- FIG. 2 is a diagram illustrating ionization energy of each hydrocarbon according to some example embodiments.
- a carbon source having relatively low ionization energy may typically be in a liquid state at room temperature.
- hydrocarbons having ionization energy equal to or less than about 10.6 eV may be benzene, specifically, benzene that is substituted with at least one alkyl group. While benzene, toluene, and meta-xylene are illustrated as hydrocarbons having ionization energy of 10.6 eV or lower in FIG. 2 , the hydrocarbons are not limited thereto. Any other hydrocarbons having ionization energy of 10.6 eV or lower may also be applied.
- FIGS. 3A and 3B are views illustrating a result of the Raman analysis of graphene grown using different carbon sources according to some example embodiments.
- a peak G may be present around (e.g., “at about”) 1590 cm ⁇ 1
- a peak D may be present around 1350 cm ⁇ 1
- a 2D peak may be present around 2700 cm ⁇ 1 .
- the graphene grown by using meta-xylene for seven minutes had a graphene structure of a strong intensity.
- the graphene grown by using methane for sixty minutes had a graphene structure of a weak intensity. That is, it is shown that by using a hydrocarbon having low ionization energy, graphene may be easily grown even for a short period of time at a low temperature.
- a ratio (D/G) of the peak D with respect to peak G of the graphene grown using meta-xylene was greater than a ratio (D/G) of the peak D with respect to peak G of the graphene grown using methane.
- graphene having better crystallinity may be grown by using a carbon source having relatively low ionization energy even at a low temperature (e.g., meta-xylene) than a carbon source having relatively high ionization energy (e.g., methane).
- FIGS. 4A, 4B, 4C, and 4D are views of a method of forming graphene, according to some example embodiments.
- a pre-treatment process may be performed on a surface 120 a of the non-catalyst substrate 120 based on using a reducing gas.
- the pre-treatment process may be performed at a low temperature.
- the pre-treatment process of the non-catalyst substrate 120 may be performed at a processing temperature equal to or lower than about 400° C. (e.g., between about 180° C. and about 400° C.).
- a processing pressure at which a pre-treatment process of the non-catalyst substrate 120 is performed may be lower than, for example, a processing pressure at which a graphene growth process which will be described later is performed.
- the pre-treatment process of the non-catalyst substrate 120 may be performed to remove impurities, oxygen, or the like remaining on the surface of the non-catalyst substrate 120 .
- charges or activation sites that each enable effective adsorption of active carbon radicals onto a surface 120 a of the non-catalyst substrate 120 may be generated.
- a method of generating charges and activation sites will be described.
- the non-catalyst substrate 120 for growing the graphene 190 is provided (e.g., located, positioned, or the like) inside a reaction chamber.
- the non-catalyst substrate 120 may refer to a substrate formed of a material that does catalyze growth of graphene.
- the non-catalyst substrate 120 may include at least one of a Group IV semiconductor material, a semiconductor compound, or an insulating material.
- the Group IV semiconductor material may include Si, Ge, or Sn.
- the semiconductor compound may include, for example, a material in which at least two elements selected from among Si, Ge, C, Zn, Cd, Al, Ga, In, B, C, N, P, S, Se, As, Sb, or Te are combined.
- the insulating material may include at least one of Si, Al, Hf, Zr, Zn, Ti, Ta, W, or Mn or at least one of an oxide, a nitride, a carbide of at least one of Si, Ni, Al, W, Ru, Co, Mn, Ti, Ta, Au, Hf, Zr, Zn, Y, Cr, Cu, Mo, or Gd, or a derivative thereof.
- the at least one of the oxide, nitride, carbide, or the derivative thereof may further include H.
- the non-catalyst substrate 120 may further include a dopant.
- a gas for pre-treatment of the non-catalyst substrate 120 (e.g., a pre-treatment gas) is injected into the reaction chamber.
- a reducing gas may be used as a pre-treatment gas.
- the reducing gas may include, for example, at least one of hydrogen, nitrogen, chlorine, fluorine, ammonia, or derivatives thereof.
- the reducing gas is not limited thereto.
- an inert gas may be additionally injected into the reaction chamber in addition to the reducing gas.
- the inert gas may include, for example, at least one of argon gas, neon gas, nitrogen gas, helium gas, krypton gas, or xenon gas.
- the inert gas is used in place of the reducing gas.
- hydrogen gas is used as the reducing gas.
- a bias (e.g., bias power) is applied (e.g., supplied) to the non-catalyst substrate 120 via a bias supply 130 (e.g., bias power supply).
- a bias applied to the non-catalyst substrate 120 may be, for example, an RF bias or a direct-current (DC) bias. Accordingly, a certain (+) bias voltage or a ( ⁇ ) bias voltage may be applied to the non-catalyst substrate 120 . To this end, bias power having a certain amount may be applied to the non-catalyst substrate 120 .
- bias power ranging from about 1 W to about 300 W may be applied to the non-catalyst substrate 120 in a pre-treatment process of the non-catalyst substrate 120 .
- bias power applied to the non-catalyst substrate 120 may vary.
- gas plasma for example, hydrogen plasma
- the bias power applied to the non-catalyst substrate 120 may be about 1 W to about 300 W.
- at least one of charges 141 or activation sites 142 may be formed on the surface 120 a of the non-catalyst substrate 120 .
- (+) charges 141 may be formed on the surface 120 a of the non-catalyst substrate 120 .
- (+) bias voltage is applied to the non-catalyst substrate 120
- (+) charges 141 may be formed on the surface 120 a of the non-catalyst substrate 120 .
- the activation sites 142 may be formed as the charges 141 move toward the non-catalyst substrate 120 to collide with the surface 120 a of the non-catalyst substrate 120 .
- the activation sites 142 may have, for example, roughness or defects. In FIG. 4B , roughness is illustrated as an example of the activation sites 142 .
- the charges 141 and/or the activation sites 142 may enable active carbon radicals to be effectively adsorbed onto the surface 120 a of the non-catalyst substrate 120 , and graphene may be directly grown on the surface 120 a of the non-catalyst substrate 120 even at a low temperature of 400° C. or lower.
- the pre-treatment process may include forming at least one of charges 141 or activation sites that induce adsorption of active carbon radicals on the surface 120 a of the non-catalyst substrate 120 .
- a reaction gas for growing the graphene 190 is injected into the reaction chamber and power for generating plasma is applied into the reaction chamber.
- a reaction gas is injected into the reaction chamber to grow the graphene 190 .
- the reaction gas may include a carbon source gas, an inert gas, and a hydrogen gas.
- the reaction gas may not include a hydrogen gas.
- a carbon source may be a hydrocarbon having ionization energy of 10.6 eV or lower, and the hydrocarbon may include a liquid precursor, which is in a liquid state at room temperature.
- the liquid precursor may be a molecular precursor including one or more aromatic molecular rings such as benzene, toluene, xylene, mesitylene, or the like or a precursor including a molecule having one or more aromatic molecular rings, such as chlorobenzene or anisole, and a functional group.
- the carbon source may include a molecular precursor including three or more aliphatic carbon bonds such as propane, propene, butane, hexane, octane, cyclohexane, or the like and a precursor including a functional group such as oxygen, nitrogen, sulfur, or the like.
- a molecular precursor including three or more aliphatic carbon bonds such as propane, propene, butane, hexane, octane, cyclohexane, or the like
- a precursor including a functional group such as oxygen, nitrogen, sulfur, or the like.
- any hydrocarbon having ionization energy of 10.6 eV or less may be used.
- the inert gas may include, for example, at least one of argon gas, neon gas, nitrogen gas, helium gas, krypton gas, or xenon gas.
- argon gas may include, for example, at least one of argon gas, neon gas, nitrogen gas, helium gas, krypton gas, or xenon gas.
- FIG. 4C some example embodiments in which acetylene gas is used as a carbon source and argon gas is used as an inert gas is illustrated.
- the power for generating plasma is applied to the reaction chamber from a plasma power supply.
- the power for generating plasma may be approximately 10 W to 4000 W.
- the plasma power supply for example, at least one RF plasma generator or at least one MW plasma generator may be used.
- a processing temperature may be about 180° C. to about 400° C.
- the processing pressure may be about 0.001 Torr to about 10 Torr.
- an electric field may be induced in the reaction chamber.
- plasma for growing the graphene 190 is formed.
- plasma of the inert gas From among the reaction gas, plasma of the inert gas generates active carbon radicals from the carbon source.
- the active carbon radicals are adsorbed onto a surface the surface 120 a of the non-catalyst substrate 120 to activate the surface 120 a of the non-catalyst substrate 120 .
- plasma of the inert gas continuously induces activation of the non-catalyst substrate 120 , and charges and activation sites may accelerate adsorption of the active carbon radicals on the surface 120 a of the non-catalyst substrate 120 .
- the ionization energy of the carbon source is as low as 10.6 eV, and thus, active carbon radicals may be easily generated also at a low temperature, for example, about 180° C. to about 400° C.
- the graphene 190 may be directly grown on the surface 120 a of the non-catalyst substrate 120 .
- the graphene 190 may be grown on the surface 120 a of the non-catalyst substrate 120 in a short period of time.
- the graphene 190 may be grown on the surface 120 a of the non-catalyst substrate 120 at a relatively high speed.
- the graphene 190 having a desired thickness may be grown in a relatively short period of time, for example, thirty minutes or less (specifically, ten minutes or less).
- the graphene 190 having a desired thickness may be formed on the surface 120 a of the non-catalyst substrate 120 in a relatively short period of time.
- the graphene 190 formed as described above may have a single-layer or multi-layer structure.
- a pre-treatment is performed on a surface of the non-catalyst substrate 120 by using a reducing gas (or a mixture gas of a reducing gas and an inert gas), and then the graphene 190 is grown on the pre-treated surface of the non-catalyst substrate 120 to thereby obtain the graphene 190 having a relatively high quality even at a low temperature.
- a reducing gas or a mixture gas of a reducing gas and an inert gas
- a method of forming graphene 190 may include pre-treating a surface 120 a of a non-catalyst substrate 120 at least partially including a material that does not catalyze growth of graphene, where the pre-treating includes forming at least one of charges or activation sites that induce adsorption of active carbon radicals on the surface of the non-catalyst substrate ( FIGS. 4A-4B ), and directly growing graphene 190 on the pre-treated surface 120 a of the non-catalyst substrate 120 ( FIG. 4D ) based on injecting a reaction gas into the reaction chamber in which the non-catalyst substrate is provided ( FIG. 4C ), the reaction gas including a carbon source having an ionization energy equal to or less than about 10.6 eV in a plasma-enhanced chemical vapor deposition (PECVD) process.
- PECVD plasma-enhanced chemical vapor deposition
- FIG. 5 is a cross-sectional view of an apparatus 500 for forming graphene according to some example embodiments.
- the apparatus 500 may perform any of the methods of forming graphene according to any of the example embodiments.
- the apparatus 500 may be, in some example embodiments, a plasma enhanced chemical vapor deposition machine configured to perform any of the methods of forming graphene according to any of the example embodiments.
- an apparatus 500 may include a gas supply 510 , a process chamber 560 , a plasma generation unit 570 , a substrate transporter 572 , a pumping system 574 , a heater 576 , a power supply 578 , and an operation station 580 .
- the process chamber 560 may include a chamber housing 520 , an upper electrode 530 in the chamber housing 520 , and a substrate support 550 in the chamber housing 520 .
- the upper electrode 530 may be connected to a gas supply 510 with conduits and gas flow controllers for providing reaction gases into the process chamber 560 .
- the substrate support 550 may be an electrostatic chuck, but is not limited thereto.
- a substrate transporter 572 such as a robot arm, may transport a substrate 540 into and out of the process chamber 560 .
- the process chamber 560 may include a gate valve that opens when the substrate transporter 572 transports the substrate 540 into or out of the process chamber 560 and closes when the process chamber 560 performs operations (e.g., vacuum processes).
- a heater 576 e.g., electric heater
- the plasma generation unit 570 may be a RF power generator and may be connected to the substrate support 550 and may be used to generate a plasma P of a reaction gas in the process chamber 560 .
- a microwave power supply may be used to generate the plasma P in the process chamber 560 .
- a pumping system 574 connected to the process chamber 560 may create a vacuum in the process chamber 560 .
- a power supply 578 (e.g., circuit) may provide electrical power to the apparatus 500 .
- the operation station 580 may control operations of the apparatus 500 .
- the operation station 580 may include a controller 582 , a memory 584 , a display 586 (e.g., monitor), and an input and output device 588 .
- the memory 584 may include a nonvolatile memory, such as a flash memory, a phase-change random access memory (PRAM), a magneto-resistive RAM (MRAM), a resistive RAM (ReRAM), or a ferro-electric RAM (FRAM), and/or a volatile memory, such as a static RAM (SRAM), a dynamic RAM (DRAM), or a synchronous DRAM (SDRAM).
- the input and output device 588 may be a keyboard and/or a touch screen.
- the memory 584 may store an operating system and may store recipe instructions that include settings (e.g., gas flow rates, temperature, time, power, pressure, etc.) for different manufacturing processes performed by the apparatus 500 .
- the memory 584 may store recipe instructions for forming a graphene product (e.g., graphene) on the substrate 540 according to one or more of the embodiments in FIGS. 1A-1C and/or 4A-4D of the present application.
- the controller 582 may be, a central processing unit (CPU), a controller, or an application-specific integrated circuit (ASIC), that when, executing recipe instructions stored in the memory 584 (for one or more of the embodiments in FIGS. 1A-1C and/or 4A-4D ) configures the controller 582 as a special purpose controller that operates apparatus 500 to form a graphene according to example embodiments on the substrate 540 .
- CPU central processing unit
- ASIC application-specific integrated circuit
- the controller 582 may be included in, may include, and/or may be implemented by, one or more instances of processing circuitry such as hardware including logic circuits; a hardware/software combination such as a processor executing software; or a combination thereof.
- processing circuitry more specifically may include, but is not limited to, a central processing unit (CPU), an arithmetic logic unit (ALU), a digital signal processor, a microcomputer, a field programmable gate array (FPGA), a System-on-Chip (SoC), a programmable logic unit, a microprocessor, application-specific integrated circuit (ASIC), etc.
- CPU central processing unit
- ALU arithmetic logic unit
- FPGA field programmable gate array
- SoC System-on-Chip
- ASIC application-specific integrated circuit
- the processing circuitry may include a non-transitory computer readable storage device, for example a solid state drive (SSD), storing a program of instructions, and a processor configured to execute the program of instructions to implement the functionality of the controller 582 .
- SSD solid state drive
- graphene may be easily grown even at a low temperature by using a carbon source having low ionization energy.
- the charges and activation sites generated in the pre-treatment process may accelerate growth of graphene to thereby form the graphene in a short period of time.
Abstract
Description
- This application claims the benefit of Korean Patent Application No. 10-2019-0053240, filed on May 7, 2019, in the Korean Intellectual Property Office, the disclosure of which is incorporated herein in its entirety by reference.
- The present disclosure relates to methods of forming graphene, and more particularly, to methods of directly forming graphene on non-catalyst substrates.
- To address the problems of the increasing resistance caused by the reduced width of metal wiring and the need for development of new metal barrier materials in the field of semiconductor devices, research into graphene is actively conducted. Graphene is a material having a hexagonal honeycomb structure in which carbon atoms are connected two-dimensionally and has a very small, atomic-scale thickness. Graphene has higher electric mobility and excellent heat characteristics compared to silicon (Si), and is also chemically stable and has a broad surface area.
- Provided are methods of directly forming graphene on non-catalyst substrates.
- According to some example embodiments, a method of forming graphene may include providing, in a reaction chamber, a non-catalyst substrate at least partially including a material that does not catalyze growth of graphene, and directly growing graphene on a surface of the non-catalyst substrate based on injecting a reaction gas into the reaction chamber, the reaction gas including a carbon source having an ionization energy equal to or less than about 10.6 eV in a plasma-enhanced chemical vapor deposition (PECVD) process.
- The growing of the graphene may be performed at a processing temperature equal to or less than about 400° C.
- The plasma may be generated based on using at least one radio frequency (RF) plasma generator or at least one microwave (MW) plasma generator.
- The non-catalyst substrate may include at least one of a Group IV semiconductor material, a semiconductor compound, or an insulating material.
- The non-catalyst substrate may further include a dopant.
- The non-catalyst substrate may include a material that includes a combination of at least two elements selected from among Si, Ge, C, Zn, Cd, Al, Ga, In, B, C, N, P, S, Se, As, Sb, or Te.
- The non-catalyst substrate may include at least one of an oxide, a nitride, a carbide of at least one of Si, Ni, Al, W, Ru, Co, Mn, Ti, Ta, Au, Hf, Zr, Zn, Y, Cr, Cu, Mo, or Gd, or a derivative thereof.
- The carbon source may include a hydrocarbon which is in a liquid state at room temperature.
- The carbon source may include at least one of a precursor including a molecular precursor, the molecular precursor including one or more aromatic molecular rings, a precursor including a molecule having one or more aromatic molecular rings and a functional group, a molecular precursor including three or more aliphatic carbon bonds, or a precursor including a functional group.
- The carbon source may include at least one of benzene, toluene, meta-xylene, propane, propene, butane, hexane, octane, cyclohexane, oxygen, nitrogen, sulfur, or phosphor.
- The reaction gas may further include at least one of an inert gas or a reducing gas.
- The graphene may include crystals having a crystal size of about 0.5 nm to about 100 nm.
- The directly growing the graphene may be performed at a pressure that is equal to or less than about 10 Torr.
- The method may further include performing a pre-treatment on a surface of the non-catalyst substrate.
- The performing the pre-treatment may include forming at least one of charges or activation sites that induce adsorption of active carbon radicals on the surface of the non-catalyst substrate.
- The performing the pre-treatment may include injecting a pre-treatment gas into the reaction chamber.
- The pre-treatment gas may include at least one of inert gas, hydrogen, nitrogen, chlorine, fluorine, ammonia, or derivatives thereof.
- An apparatus may include a plasma enhanced chemical vapor deposition machine configured to perform the method.
- The performing the pre-treatment may include supplying a bias power to the non-catalyst substrate, the bias power ranging from about 1 W to about 300 W.
- According to some example embodiments, a method of forming graphene may include pre-treating a surface of a non-catalyst substrate at least partially including a material that does not catalyze growth of graphene, pre-treating including forming at least one of charges or activation sites that induce adsorption of active carbon radicals on the surface of the non-catalyst substrate; and directly growing graphene on the pre-treated surface of the non-catalyst substrate based on injecting a reaction gas into a reaction chamber in which the non-catalyst substrate is provided, the reaction gas including a carbon source having an ionization energy equal to or less than about 10.6 eV in a plasma-enhanced chemical vapor deposition (PECVD) process.
- The pre-treating the non-catalyst substrate may include placing the non-catalyst substrate including the pre-treated surface in the reaction chamber, injecting a pre-treatment gas into the reaction chamber, and supplying a bias power to the non-catalyst substrate, the bias power ranging from about 1 W to about 300 W.
- The pre-treatment gas may include at least one of inert gas, hydrogen, nitrogen, chlorine, fluorine, ammonia, or derivatives thereof.
- The growing of the graphene may be performed at a processing temperature equal to or less than about 400° C.
- The plasma may be generated based on using at least one radio frequency (RF) plasma generator or at least one microwave (MW) plasma generator.
- The non-catalyst substrate may include at least one of a Group IV semiconductor material, a semiconductor compound, or an insulating material.
- The non-catalyst substrate may further include a dopant.
- The non-catalyst substrate may include a material that includes a combination of at least two elements selected from among Si, Ge, C, Zn, Cd, Al, Ga, In, B, C, N, P, S, Se, As, Sb, and Te.
- The non-catalyst substrate may include at least one of an oxide, a nitride, a carbide of at least one of Si, Ni, Al, W, Ru, Co, Mn, Ti, Ta, Au, Hf, Zr, Zn, Y, Cr, Cu, Mo, or Gd, or a derivative thereof.
- The carbon source may include a hydrocarbon which is in a liquid state at room temperature.
- The carbon source may include at least one of a precursor including a molecular precursor, the molecular precursor including one or more aromatic molecular rings, a precursor including a molecule having one or more aromatic molecular rings and a functional group, a molecular precursor including three or more aliphatic carbon bonds, or a precursor including a functional group.
- The carbon source may include at least one of benzene, toluene, meta-xylene, propane, propene, butane, hexane, octane, cyclohexane, oxygen, nitrogen, sulfur, or phosphor.
- The reaction gas may further include at least one of an inert gas or a reducing gas.
- The graphene may include crystals having a crystal size of about 0.5 nm to about 100 nm.
- The directly growing the graphene may be performed at a pressure that is equal to or less than about 10 Torr.
- An apparatus may include a plasma enhanced chemical vapor deposition machine configured to perform the method.
- These and/or other aspects will become apparent and more readily appreciated from the following description of some example embodiments, taken in conjunction with the accompanying drawings in which:
-
FIGS. 1A, 1B, and 1C are views of a method of forming graphene, according to some example embodiments; -
FIG. 2 is a diagram illustrating ionization energy of each hydrocarbon according to some example embodiments; -
FIGS. 3A and 3B are views illustrating a result of the Raman analysis of graphene grown using different carbon sources according to some example embodiments; -
FIGS. 4A, 4B, 4C, and 4D are views of a method of forming graphene, according to some example embodiments; and -
FIG. 5 is a cross-sectional view of an apparatus for forming graphene according to some example embodiments. - Reference will now be made in detail to example embodiments, some example embodiments of which are illustrated in the accompanying drawings, wherein like reference numerals refer to like elements throughout and sizes of constituent elements may be exaggerated for convenience of explanation and the clarity of the specification. In this regard, some example embodiments may have different forms and should not be construed as being limited to the descriptions set forth herein. Accordingly, some example embodiments are merely described below, by referring to the figures, to explain aspects of the present description. As used herein, the term “and/or” includes any and all combinations of one or more of the associated listed items (e.g., A, B, and C). Expressions such as “at least one of,” when preceding a list of elements, modify the entire list of elements and do not modify the individual elements of the list. For example, “at least one of A, B, and C,” and “at least one of A, B, or C” may be construed as covering any one of the following combinations: A; B; A and B; A and C; B and C; and A, B, and C.”
- It will also be understood that when an element is referred to as being “on” or “above” another element, the element may be in direct contact with the other element or other intervening elements may be present. An expression used in the singular encompasses the expression of the plural, unless it has a clearly different meaning in the context. It should be understood that, when a part “comprises” or “includes” an element in the specification, unless otherwise defined, other elements are not excluded from the part and the part may further include other elements. The use of the terms “the” and similar referents in the context are to be construed to cover both the singular and the plural.
- In some example embodiments, graphene (nanocrystalline graphene) and a method of directly growing graphene on a surface of a non-catalyst substrate in a plasma-enhanced chemical vapor deposition (PECVD) method will be described.
-
FIGS. 1A, 1B, and 1C are views of a method of forming graphene, according to some example embodiments. - Referring to
FIG. 1A , a reaction gas for growing graphene 190 (e.g., a layer of graphene) (FIG. 1C ) is injected into a reaction chamber (not shown) in which anon-catalyst substrate 120 is provided (e.g., located), and power to generate plasma is applied (e.g., supplied). - First, the
non-catalyst substrate 120 is provided in the reaction chamber (e.g., placed in the reaction chamber). Thenon-catalyst substrate 120 includes a substrate formed of (e.g., at least partially comprising) a material that does not catalyze growth of graphene (e.g., is configured to not catalyze growth of graphene). Accordingly, thenon-catalyst substrate 120 may be configured to not catalyze growth of graphene on an upper surface,surface 120 a, of thenon-catalyst substrate 120. For example, thenon-catalyst substrate 120 may include a substrate that does not include a metal. Thenon-catalyst substrate 120 may include at least one of a Group IV semiconductor material, a semiconductor compound, or an insulating material. In detail, the Group IV semiconductor material may include Si, Ge, or Sn. The semiconductor compound may include, for example, a material that includes a combination of at least two elements selected from among Si, Ge, C, Zn, Cd, Al, Ga, In, B, C, N, P, S, Se, As, Sb, or Te. - The insulating material may include at least one of Si, Al, Hf, Zr, Zn, Ti, Ta, W, or Mn or at least one of an oxide, a nitride, a carbide of at least one of Si, Ni, Al, W, Ru, Co, Mn, Ti, Ta, Au, Hf, Zr, Zn, Y, Cr, Cu, Mo, or Gd, or a derivative thereof. Accordingly, the
non-catalyst substrate 120 may include at least one of an oxide, a nitride, a carbide of at least one of Si, Ni, Al, W, Ru, Co, Mn, Ti, Ta, Au, Hf, Zr, Zn, Y, Cr, Cu, Mo, or Gd, or a derivative thereof. The at least one of the oxide, nitride, carbide, or the derivative thereof may further include H. Thenon-catalyst substrate 120 may further include a dopant. The materials of thenon-catalyst substrate 120 described above are examples, and thenon-catalyst substrate 120 may be formed of (e.g., at least partially comprise) a material that does not catalyze the growth of graphene. - Next, a reaction gas is injected into the reaction chamber to grow the
graphene 190. The reaction gas may include a carbon source supplying carbon to grow thegraphene 190. The carbon source may be a hydrocarbon having ionization energy equal to or less than about 10.6 eV, for example between about 1.2 eV and about 10.6 eV. - When the terms “about” or “substantially” are used in this specification in connection with a numerical value, it is intended that the associated numerical value include a tolerance of ±10% around the stated numerical value. When ranges are specified, the range includes all values therebetween such as increments of 0.1%.
- The carbon source may include a liquid precursor, which is in a liquid state at room temperature. The carbon source may include a hydrocarbon which is in a liquid state at room temperature (e.g., about 20° C. to about 25° C.). For example, the liquid precursor may be a molecular precursor including one or more aromatic molecular rings such as benzene, toluene, xylene, mesitylene, or the like or a precursor including a molecule having one or more aromatic molecular rings, such as chlorobenzene or anisole (methyl phenyl ether), and a functional group. In some example embodiments, the carbon source may include a molecular precursor including three or more aliphatic carbon bonds such as propane, propene, butane, hexane, octane, cyclohexane, or the like and a precursor including a functional group such as oxygen, nitrogen, sulfur, or the like. In some example embodiments, the carbon source may include at least one of benzene, toluene, meta-xylene, propane, propene, butane, hexane, octane, cyclohexane, oxygen, nitrogen, sulfur, or phosphor. However, these are merely examples, and any hydrocarbon having ionization energy of about 10.6 eV or less (e.g., between about 1.2 eV and about 10.6 eV) may be used.
- The reaction gas may further include at least one of an inert gas or a hydrogen gas. The inert gas may include, for example, at least one of argon gas, neon gas, nitrogen gas, helium gas, krypton gas, or xenon gas.
FIG. 1A shows an example in which the reaction gas includes a carbon source, inert gas, and hydrogen gas, wherein meta-xylene is used as the carbon source and argon gas is used as the inert gas. A mixing ratio of the reaction gas injected into the reaction chamber may be variously modified according to the growth conditions of the graphene. - Next, power for generating plasma is applied (e.g., supplied) to the reaction chamber from a plasma power supply (not shown). Here, the power for generating plasma may be about 10 W to about 4,000 W. However, the power is not limited thereto.
- As the plasma power supply, for example, a radio frequency (RF) plasma generator or a microwave (MW) plasma generator, may be used. Restated, the plasma-enhanced chemical vapor deposition (PECVD) process may utilize a plasma that may be generated based on using at least one radio frequency (RF) plasma generate or at least one microwave (MW) plasma generator. To grow the
graphene 190, the RF plasma generator may generate RF plasma having a frequency range of, for example, about 3 MHz to about 100 MHz, and the MW plasma generator may generate MW plasma having a frequency range of, for example, about 0.7 to about 2.5 GHz. The frequency ranges above are examples, and other frequency ranges may also be used. Meanwhile, a plurality of RF plasma generators or a plurality of MW plasma generators may be used as a plasma power supply. - When power for generating plasma is applied (e.g., supplied) from the plasma power supply into the reaction chamber, an electric field may be induced in the reaction chamber. When an electric field is induced after the reaction gas is injected, plasma for growing graphene is formed.
- When growing graphene by using plasma, a mixing ratio of reaction gases injected into the reaction chamber, that is, a volume ratio of a carbon source, an inert gas, and a hydrogen gas may be, for example, approximately about 1:about 0.01 to about 5,000:about 0 to about 300. The volume ratio of the carbon source, the inert gas, and the hydrogen gas included in the reaction gas may be appropriately adjusted according to different growth conditions.
- A processing temperature for growing graphene may be equal to or less than about 400° C., which is lower than a temperature used in a chemical vapor deposition (CVD) process. For example, a processing temperature in the reaction chamber may be about 180° C. to about 400° C. A processing pressure for growing graphene may be equal to or less than about 10 Torr. For example, the processing pressure may be about 0.001 Torr to about 10 Torr. However, the above-described processing pressure is an example, and other processing pressures may also be used.
- Referring to
FIG. 1B , active carbon radicals (C*) are generated by plasma of a reaction gas, in which a carbon source, an inert gas, and a hydrogen gas are mixed and are adsorbed onto a surface of thenon-catalyst substrate 120. As the carbon source has ionization energy of about 10.6 eV, active carbon radicals (C*) are easily generated at a relatively low temperature, and the active carbon radicals (C*) are adsorbed onto the surface of thenon-catalyst substrate 120 to activate the surface of thenon-catalyst substrate 120. Also, as plasma of the inert gas continuously induces activation of thenon-catalyst substrate 120, adsorption of the active carbon radicals (C*) onto thesurface 120 a of thenon-catalyst substrate 120 may be accelerated. Moreover, due to the relatively low ionization energy, graphene may be directly grown on a substrate without a catalyst. - Referring to
FIG. 1C , as adsorption of the active carbon radicals (C*) onto thesurface 120 a of thenon-catalyst substrate 120 is accelerated even at a low temperature, thegraphene 190 may be grown on the surface of thenon-catalyst substrate 120. According to some example embodiments, as the ionization energy of the carbon source is as low as 10.6 eV, active carbon radicals may be easily generated even at a low temperature, for example, at a temperature equal to or less than about 400° C. (e.g., about 180° C. to about 400° C.). Thus, thegraphene 190 may be directly grown on thesurface 120 a of thenon-catalyst substrate 120. The grown graphene may include nano-scale crystals. For example, thegraphene 190 may include crystals having a size equal to or less than about 100 nm. In detail, thegraphene 190 may include crystals having a size of about 0.5 nm to about 100 nm. - Accordingly, as shown in
FIGS. 1A-C , a method of forming graphene according to some example embodiments may include providing, in a reaction chamber, anon-catalyst substrate 120 at least partially including a material that does not catalyze growth of graphene; and directly growinggraphene 190 on asurface 120 a of the non-catalyst substrate 120 (FIG. 1C ) based on injecting a reaction gas into the reaction chamber (FIG. 1A ), the reaction gas including a carbon source having an ionization energy equal to or less than about 10.6 eV in a plasma-enhanced chemical vapor deposition (PECVD) process. -
FIG. 2 is a diagram illustrating ionization energy of each hydrocarbon according to some example embodiments. As illustrated inFIG. 2 , a carbon source having relatively low ionization energy may typically be in a liquid state at room temperature. In addition, hydrocarbons having ionization energy equal to or less than about 10.6 eV may be benzene, specifically, benzene that is substituted with at least one alkyl group. While benzene, toluene, and meta-xylene are illustrated as hydrocarbons having ionization energy of 10.6 eV or lower inFIG. 2 , the hydrocarbons are not limited thereto. Any other hydrocarbons having ionization energy of 10.6 eV or lower may also be applied. -
FIGS. 3A and 3B are views illustrating a result of the Raman analysis of graphene grown using different carbon sources according to some example embodiments. In general, in a Raman spectrum, a peak G may be present around (e.g., “at about”) 1590 cm−1, a peak D may be present around 1350 cm−1, and a 2D peak may be present around 2700 cm−1. - As illustrated in
FIG. 3A , the graphene grown by using meta-xylene for seven minutes had a graphene structure of a strong intensity. However, the graphene grown by using methane for sixty minutes had a graphene structure of a weak intensity. That is, it is shown that by using a hydrocarbon having low ionization energy, graphene may be easily grown even for a short period of time at a low temperature. - In addition, as illustrated in
FIG. 3B , even when a width WD of peak D of the graphene grown by using meta-xylene is less than a width WD of peak D of the graphene grown by using methane, a ratio (D/G) of the peak D with respect to peak G of the graphene grown using meta-xylene was greater than a ratio (D/G) of the peak D with respect to peak G of the graphene grown using methane. This may indicate that graphene having better crystallinity may be grown by using a carbon source having relatively low ionization energy even at a low temperature (e.g., meta-xylene) than a carbon source having relatively high ionization energy (e.g., methane). -
FIGS. 4A, 4B, 4C, and 4D are views of a method of forming graphene, according to some example embodiments. - Referring to
FIG. 4A , before growing graphene, a pre-treatment process may be performed on asurface 120 a of thenon-catalyst substrate 120 based on using a reducing gas. The pre-treatment process may be performed at a low temperature. For example, the pre-treatment process of thenon-catalyst substrate 120 may be performed at a processing temperature equal to or lower than about 400° C. (e.g., between about 180° C. and about 400° C.). In addition, a processing pressure at which a pre-treatment process of thenon-catalyst substrate 120 is performed may be lower than, for example, a processing pressure at which a graphene growth process which will be described later is performed. - The pre-treatment process of the
non-catalyst substrate 120 may be performed to remove impurities, oxygen, or the like remaining on the surface of thenon-catalyst substrate 120. In some example embodiments, in the pre-treatment process, charges or activation sites that each enable effective adsorption of active carbon radicals onto asurface 120 a of thenon-catalyst substrate 120 may be generated. Hereinafter, a method of generating charges and activation sites will be described. - First, the
non-catalyst substrate 120 for growing thegraphene 190 is provided (e.g., located, positioned, or the like) inside a reaction chamber. Thenon-catalyst substrate 120 may refer to a substrate formed of a material that does catalyze growth of graphene. For example, thenon-catalyst substrate 120 may include at least one of a Group IV semiconductor material, a semiconductor compound, or an insulating material. In detail, the Group IV semiconductor material may include Si, Ge, or Sn. The semiconductor compound may include, for example, a material in which at least two elements selected from among Si, Ge, C, Zn, Cd, Al, Ga, In, B, C, N, P, S, Se, As, Sb, or Te are combined. - The insulating material may include at least one of Si, Al, Hf, Zr, Zn, Ti, Ta, W, or Mn or at least one of an oxide, a nitride, a carbide of at least one of Si, Ni, Al, W, Ru, Co, Mn, Ti, Ta, Au, Hf, Zr, Zn, Y, Cr, Cu, Mo, or Gd, or a derivative thereof. The at least one of the oxide, nitride, carbide, or the derivative thereof may further include H. The
non-catalyst substrate 120 may further include a dopant. - Next, referring to
FIG. 4A , a gas for pre-treatment of the non-catalyst substrate 120 (e.g., a pre-treatment gas) is injected into the reaction chamber. Here, a reducing gas may be used as a pre-treatment gas. The reducing gas may include, for example, at least one of hydrogen, nitrogen, chlorine, fluorine, ammonia, or derivatives thereof. However, the reducing gas is not limited thereto. In addition, an inert gas may be additionally injected into the reaction chamber in addition to the reducing gas. The inert gas may include, for example, at least one of argon gas, neon gas, nitrogen gas, helium gas, krypton gas, or xenon gas. In some example embodiments, the inert gas is used in place of the reducing gas. Referring toFIG. 4A , hydrogen gas is used as the reducing gas. - Next, a bias (e.g., bias power) is applied (e.g., supplied) to the
non-catalyst substrate 120 via a bias supply 130 (e.g., bias power supply). A bias applied to thenon-catalyst substrate 120 may be, for example, an RF bias or a direct-current (DC) bias. Accordingly, a certain (+) bias voltage or a (−) bias voltage may be applied to thenon-catalyst substrate 120. To this end, bias power having a certain amount may be applied to thenon-catalyst substrate 120. For example, bias power ranging from about 1 W to about 300 W may be applied to thenon-catalyst substrate 120 in a pre-treatment process of thenon-catalyst substrate 120. However, this is merely an example, and the bias power applied to thenon-catalyst substrate 120 may vary. - Referring to
FIG. 4B , while a bias is applied to thenon-catalyst substrate 120, when plasma power is applied into the reaction chamber, gas plasma (for example, hydrogen plasma) may be generated in the reaction chamber. The bias power applied to thenon-catalyst substrate 120 may be about 1 W to about 300 W. When gas plasma is generated in the reaction chamber while a bias is applied to thenon-catalyst substrate 120 as described above, at least one ofcharges 141 oractivation sites 142 may be formed on thesurface 120 a of thenon-catalyst substrate 120. - For example, while (e.g., simultaneously with) a (−) bias voltage is applied to the
non-catalyst substrate 120, (+) charges 141 may be formed on thesurface 120 a of thenon-catalyst substrate 120. While a (+) bias voltage is applied to thenon-catalyst substrate 120, (−)charges 141 may be formed on thesurface 120 a of thenon-catalyst substrate 120. Theactivation sites 142 may be formed as thecharges 141 move toward thenon-catalyst substrate 120 to collide with thesurface 120 a of thenon-catalyst substrate 120. Theactivation sites 142 may have, for example, roughness or defects. InFIG. 4B , roughness is illustrated as an example of theactivation sites 142. - The
charges 141 and/or theactivation sites 142 may enable active carbon radicals to be effectively adsorbed onto thesurface 120 a of thenon-catalyst substrate 120, and graphene may be directly grown on thesurface 120 a of thenon-catalyst substrate 120 even at a low temperature of 400° C. or lower. Accordingly, the pre-treatment process may include forming at least one ofcharges 141 or activation sites that induce adsorption of active carbon radicals on thesurface 120 a of thenon-catalyst substrate 120. - After the pre-treatment process of the
non-catalyst substrate 120 is completed, as illustrated inFIG. 4C , a reaction gas for growing thegraphene 190 is injected into the reaction chamber and power for generating plasma is applied into the reaction chamber. - In detail, first, a reaction gas is injected into the reaction chamber to grow the
graphene 190. The reaction gas may include a carbon source gas, an inert gas, and a hydrogen gas. In some example embodiments, the reaction gas may not include a hydrogen gas. - A carbon source may be a hydrocarbon having ionization energy of 10.6 eV or lower, and the hydrocarbon may include a liquid precursor, which is in a liquid state at room temperature. In addition, the liquid precursor may be a molecular precursor including one or more aromatic molecular rings such as benzene, toluene, xylene, mesitylene, or the like or a precursor including a molecule having one or more aromatic molecular rings, such as chlorobenzene or anisole, and a functional group. In some example embodiments, the carbon source may include a molecular precursor including three or more aliphatic carbon bonds such as propane, propene, butane, hexane, octane, cyclohexane, or the like and a precursor including a functional group such as oxygen, nitrogen, sulfur, or the like. However, these are merely examples, and any hydrocarbon having ionization energy of 10.6 eV or less may be used.
- The inert gas may include, for example, at least one of argon gas, neon gas, nitrogen gas, helium gas, krypton gas, or xenon gas. In
FIG. 4C , some example embodiments in which acetylene gas is used as a carbon source and argon gas is used as an inert gas is illustrated. - Next, power for generating plasma is applied to the reaction chamber from a plasma power supply. Here, the power for generating plasma may be approximately 10 W to 4000 W. As the plasma power supply, for example, at least one RF plasma generator or at least one MW plasma generator may be used. A processing temperature may be about 180° C. to about 400° C. For example, the processing pressure may be about 0.001 Torr to about 10 Torr.
- When power for generating plasma is applied from the plasma power supply into the reaction chamber, an electric field may be induced in the reaction chamber. When an electric field is induced after the reaction gas is injected, plasma for growing the
graphene 190 is formed. - From among the reaction gas, plasma of the inert gas generates active carbon radicals from the carbon source. The active carbon radicals are adsorbed onto a surface the
surface 120 a of thenon-catalyst substrate 120 to activate thesurface 120 a of thenon-catalyst substrate 120. Also, plasma of the inert gas continuously induces activation of thenon-catalyst substrate 120, and charges and activation sites may accelerate adsorption of the active carbon radicals on thesurface 120 a of thenon-catalyst substrate 120. The ionization energy of the carbon source is as low as 10.6 eV, and thus, active carbon radicals may be easily generated also at a low temperature, for example, about 180° C. to about 400° C. Thus, thegraphene 190 may be directly grown on thesurface 120 a of thenon-catalyst substrate 120. - Referring to
FIG. 4D , as adsorption of the active carbon radical on thesurface 120 a of thenon-catalyst substrate 120 is accelerated, thegraphene 190 may be grown on thesurface 120 a of thenon-catalyst substrate 120 in a short period of time. - The
graphene 190 may be grown on thesurface 120 a of thenon-catalyst substrate 120 at a relatively high speed. For example, thegraphene 190 having a desired thickness may be grown in a relatively short period of time, for example, thirty minutes or less (specifically, ten minutes or less). As described above, thegraphene 190 having a desired thickness may be formed on thesurface 120 a of thenon-catalyst substrate 120 in a relatively short period of time. Thegraphene 190 formed as described above may have a single-layer or multi-layer structure. - According to some example embodiments, a pre-treatment is performed on a surface of the
non-catalyst substrate 120 by using a reducing gas (or a mixture gas of a reducing gas and an inert gas), and then thegraphene 190 is grown on the pre-treated surface of thenon-catalyst substrate 120 to thereby obtain thegraphene 190 having a relatively high quality even at a low temperature. - Accordingly, as shown in
FIGS. 4A-4D , a method of forminggraphene 190 according to some example embodiments may include pre-treating asurface 120 a of anon-catalyst substrate 120 at least partially including a material that does not catalyze growth of graphene, where the pre-treating includes forming at least one of charges or activation sites that induce adsorption of active carbon radicals on the surface of the non-catalyst substrate (FIGS. 4A-4B ), and directly growinggraphene 190 on thepre-treated surface 120 a of the non-catalyst substrate 120 (FIG. 4D ) based on injecting a reaction gas into the reaction chamber in which the non-catalyst substrate is provided (FIG. 4C ), the reaction gas including a carbon source having an ionization energy equal to or less than about 10.6 eV in a plasma-enhanced chemical vapor deposition (PECVD) process. -
FIG. 5 is a cross-sectional view of anapparatus 500 for forming graphene according to some example embodiments. Theapparatus 500 may perform any of the methods of forming graphene according to any of the example embodiments. Theapparatus 500 may be, in some example embodiments, a plasma enhanced chemical vapor deposition machine configured to perform any of the methods of forming graphene according to any of the example embodiments. - Referring to
FIG. 5 , anapparatus 500 may include agas supply 510, aprocess chamber 560, aplasma generation unit 570, asubstrate transporter 572, apumping system 574, aheater 576, apower supply 578, and anoperation station 580. Theprocess chamber 560 may include achamber housing 520, anupper electrode 530 in thechamber housing 520, and asubstrate support 550 in thechamber housing 520. Theupper electrode 530 may be connected to agas supply 510 with conduits and gas flow controllers for providing reaction gases into theprocess chamber 560. Thesubstrate support 550 may be an electrostatic chuck, but is not limited thereto. - A
substrate transporter 572, such as a robot arm, may transport asubstrate 540 into and out of theprocess chamber 560. Theprocess chamber 560 may include a gate valve that opens when thesubstrate transporter 572 transports thesubstrate 540 into or out of theprocess chamber 560 and closes when theprocess chamber 560 performs operations (e.g., vacuum processes). A heater 576 (e.g., electric heater) may control the temperature of thesubstrate support 550, inner wall ofprocess chamber 560, andupper electrode 530. Theplasma generation unit 570 may be a RF power generator and may be connected to thesubstrate support 550 and may be used to generate a plasma P of a reaction gas in theprocess chamber 560. In some example embodiments, a microwave power supply may be used to generate the plasma P in theprocess chamber 560. Apumping system 574 connected to theprocess chamber 560 may create a vacuum in theprocess chamber 560. A power supply 578 (e.g., circuit) may provide electrical power to theapparatus 500. - The
operation station 580 may control operations of theapparatus 500. Theoperation station 580 may include acontroller 582, amemory 584, a display 586 (e.g., monitor), and an input andoutput device 588. Thememory 584 may include a nonvolatile memory, such as a flash memory, a phase-change random access memory (PRAM), a magneto-resistive RAM (MRAM), a resistive RAM (ReRAM), or a ferro-electric RAM (FRAM), and/or a volatile memory, such as a static RAM (SRAM), a dynamic RAM (DRAM), or a synchronous DRAM (SDRAM). The input andoutput device 588 may be a keyboard and/or a touch screen. - The
memory 584 may store an operating system and may store recipe instructions that include settings (e.g., gas flow rates, temperature, time, power, pressure, etc.) for different manufacturing processes performed by theapparatus 500. Thememory 584 may store recipe instructions for forming a graphene product (e.g., graphene) on thesubstrate 540 according to one or more of the embodiments inFIGS. 1A-1C and/or 4A-4D of the present application. - The
controller 582 may be, a central processing unit (CPU), a controller, or an application-specific integrated circuit (ASIC), that when, executing recipe instructions stored in the memory 584 (for one or more of the embodiments inFIGS. 1A-1C and/or 4A-4D ) configures thecontroller 582 as a special purpose controller that operatesapparatus 500 to form a graphene according to example embodiments on thesubstrate 540. - The
controller 582 may be included in, may include, and/or may be implemented by, one or more instances of processing circuitry such as hardware including logic circuits; a hardware/software combination such as a processor executing software; or a combination thereof. For example, the processing circuitry more specifically may include, but is not limited to, a central processing unit (CPU), an arithmetic logic unit (ALU), a digital signal processor, a microcomputer, a field programmable gate array (FPGA), a System-on-Chip (SoC), a programmable logic unit, a microprocessor, application-specific integrated circuit (ASIC), etc. In some example embodiments, the processing circuitry may include a non-transitory computer readable storage device, for example a solid state drive (SSD), storing a program of instructions, and a processor configured to execute the program of instructions to implement the functionality of thecontroller 582. - According to some example embodiments, graphene may be easily grown even at a low temperature by using a carbon source having low ionization energy. The charges and activation sites generated in the pre-treatment process may accelerate growth of graphene to thereby form the graphene in a short period of time.
- It should be understood that example embodiments described herein should be considered in a descriptive sense only and not for purposes of limitation. Descriptions of features or aspects within each example embodiment should typically be considered as available for other similar features or aspects in other example embodiments. While some example embodiments have been described with reference to the figures, it will be understood by those of ordinary skill in the art that various changes in form and details may be made therein without departing from the spirit and scope as defined by the following claims.
Claims (35)
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